Chemical Metrology and the Concept of Certified Reference Materials (CRMs)

The use of reference materials makes possible the transfer of the values of measured or assigned
quantities between testing, analytical and measurement laboratories. Such materials are widely
used for the calibration of measuring equipment and for the evaluation or validation of
measurement procedures. In certain cases, they enable properties to be expressed conveniently in
arbitrary units.

There are an increasing number of reference material producers, and a demonstration of their
scientific and technical competence is now a basic requirement for ensuring the quality of
reference materials. The demand for new reference materials of higher quality is increasing as a
consequence of both the increased precision of measuring equipment and the requirement for
more accurate and reliable data in the scientific and technological disciplines.

Some previously acceptable reference materials may not meet these more stringent requirements.
It is, therefore, not only necessary for reference material producers to supply information about
their materials in the form of reports, certificates and statements, but also to demonstrate their
competence in producing reference materials of appropriate quality.

In order to be comparable across borders and over time, measurements need be traceable to
appropriate and stated references. CRMs play a key role in implementing the concept of
traceability of measurement results in chemistry, biology and physics among other sciences
dealing with materials and/or samples. Laboratories use these CRMs as readily accessible
measurement standards to establish traceability of their measurement results to international
standards. The property values carried by a CRM can be made traceable to SI units or other
internationally agreed units during production.

Concept of traceability
The term traceability is increasingly used to describe the reliability of measurements, but it is not
always clear what is meant. Essentially, traceability implies an unbroken path (with stated
uncertainties) to some higher level of accuracy or authority. In an absolute sense, this means to
the base system of measurement units [International System of Units (SI)] or their derivatives.
However, it has been more generally defined in the International Vocabulary of Basic and
General Terms in Metrology (VIM) as “the property of a result of a measurement whereby it can
be related to appropriate standards, generally international or national standards, through an
unbroken chain of comparison.” In other words, when the result of a measurement is described
as traceable, it is essential to specify to what (values of) “appropriate standards” traceability has
been established. It may be to a base unit of the SI (such as the ampere), to a mass fraction
number, to a defined scale (such as pH or hardness) or to a value resulting from the use of a
method described in a national or International Standard.
In the case of reference materials for physical properties, it is usually possible to establish
traceability via a series of instrument calibrations to the appropriate base units of the SI. For
example, the certification of a reference material for specific heat capacity is based on
measurements of electrical energy, temperature and mass, all of which are readily traceable to
the SI by means of instruments calibrated by or traceable to values obtained at national
metrology laboratories.

In the case of reference materials for chemical composition, establishing traceability often
involves more steps. For example, the analyte of interest is usually determined by the physical
response of an analytical instrument only after carrying out a number of processes such as
sampling, dissolution or extraction, as well as separation by chromatography or more traditional
wet-chemical methods. Any or all of these processes may constitute links in the traceability
chain, each with its own uncertainty. The analytical chemist must therefore assess how efficient
each process has been in completely retaining the analyte, either unchanged or stoichiometrically
converted to another chemical species up to the point that the traceability chain may be broken,
and in separating it from substances which interfere with the final instrumental measurement.

When the property is expressed in terms of the amount of substance, the analyst is faced with a
particular problem. Because of the extensive use of a balance in a chemical laboratory, the
property values of most reference materials certified for chemical composition are expressed as
mass fractions or mass/volume per mass (concentration), rather than amount of substance which
must be expressed in moles/mass.

However, working in mass is a very good approximation of working in moles. The reference
material producer is therefore concerned with demonstrating that the methods used are the most
reliable available for the determination of a particular analyte in a particular matrix and defining
the units used, for example, grams of lead per gram of blood, or grams of DDT per gram of
animal tissue.

Certification of Reference Materials

As noted in the main text, ISO Guide 35 recognizes four main procedures for the certification of
reference materials:
a) measurement by a single, primary, definitive method in a single laboratory;
b) measurement by two or more independent reference methods in one laboratory;
c) measurement by a network of qualified laboratories using one or more methods of
demonstrable accuracy;
d) a method-specific approach (interlaboratory study) giving only method-specific assessed
property values.

A primary definitive method is considered to be one where the property “is either directly
measured in terms of the base units of measurement or indirectly related to the base units through
physical or chemical theory expressed in exact mathematical equations. The term can thus be
used to include analytical chemical methods even where the result is not necessarily “in
accordance with a definition of the unit” as required by VIM. Even where such a high quality
chemical analytical method is available, it is desirable that two or more analysts make
independent determinations, preferably with different experimental facilities.

Certification by interlaboratory testing presupposes the existence of a number of equally capable

laboratories employing methods which have been independently validated, and implies that
differences between individual results are statistical in nature and can therefore be treated by
purely statistical procedures. Although this approach to certification is often unavoidable, it
frequently provides only comparability between laboratories and can lead to apparent authority
being given to wrong values, especially if the statistical treatment is allowed to predominate over
chemical wisdom and judgment. A subset of this procedure is when the analysis is method-
specific.

The traceability of reference materials can therefore range from a rigorous chain of instrumental
calibrations back to the base units of the SI to the use of a well-defined reference method. In
each case, the reference material producer needs to consider how to apply the relevant principle.
What is essential, particularly for all certified reference materials, is that the certificate contains a
statement of traceability indicating the principles and procedures on which the property values
(together with their measurement uncertainties) are based. A numerical value without this
additional information is generally considered unacceptable in a reference material certificate.